Alkyl amindosulfinic acid(bis-alkylamine)salts and method for their preparation

ABSTRACT

New aliphatic imidodisulfinic acid (aliphatic amine) salts are prepared by reacting a primary aliphatic amine or an alkanolamine having a primary amino group with SO2 under anhydrous conditions and in the absence of oxygen. The compounds reacts with Cu, Pb, Hg and other inorganic cations to form colored solutions or precipitates. They are useful as analytical reagents for metal ions.

Unite States atent [191 Frevel et al.

[ ALKYL AMINDOSULFINIC ACTD (BIS-ALKYLAMINE) SALTS AND METHOD FOR THEIR PREPARATION [75] Inventors: Ludo K. Frevel, Midland; Leonard J. Kressley, Saginaw, both of Mich.

[73] Assignee: The Dow Chemical Company,

Midland, Mich.

[22] Filed: Feb. 14, 1972 [21] Appl. No.: 226,290

Related US. Application Data [62] Division of Ser. No. 764,949, Oct. 3, i968, Pat. No.

[52] US. Cl. 26fl/50L12 [51] Int. Cl. C07c 145/00 [58] Field of Search 260/50l.12, 465.5

[56] References Cited OTHER PUBLICATIONS l-lata et al., Nature, Vol. 203, pp. 1378 (Sept. 1964).

Makranczy et al., Chemical Abstracts, Vol. 58, col. 6252 (April 1963).

Primary Examiner-Leon Zitver Assistant Examiner-Michael W. Glynn Attorney, Agent, or FirmStephen Hoynak 5 7 ABSTRACT 18 Claims, N0 Drawings ALKYIL AMINDOSULFINIC ACED (BIS-ALKYLAMINE) SALTS AND METHOD FOR THEIR PREPARATION This is a division of application Ser. No. 764,949, filed Oct. 3, 1968, now U.S. Pat. No. 3,708,526.

This invention relates to new aliphatic imidodisulfinic acid (aliphatic amine) salts having the generic O R NH; 'o-d-N- -o Z wherein R and R each represents an open chain saturatedhydrocarbon group of l to 20 C atoms, a cycloaliphatic hydrocarbon group having 5 to 8 ring C atoms, a hydroxylated open chain hydrocarbon group of 2 to 20 C atoms, a hydroxylated cycloaliphatic hydrocarbon group having 5 to 8 ring C atoms, and halogen, cyano or alkoxy substituted derivatives of said hydrocarbon groups, and Z represents H or an H N(R group where R is the same as R and R with the further proviso that when Z is H, R, and R each represents a hydroxylated open chain or cycloaliphatic hydrocarbon group as above defined, and to methods of preparing the compounds by reacting a primary aliphatic amine or primary aminoalcohol with S0 under substantially anhydrous conditions and in an inert atmosphere at temper- .a yrs Prh h ,dsssmp s io 9 1 .net.thasaltsstschanged from green to light brown. No precipitate iformed but a somewhat oily film developed on the surface of the solution. The remaining compounds of this invention also form colored compounds or precipitates with mercuric ions. Cupric and lead ions also form precipitates or colored solutions with the compounds.

The aliphatic imidodisulfinic acid (aliphatic amine) salts are decomposed by strong acids with the libera- The new compounds are soluble in water and, in

.ll flz 529.13 912-...

in which the ring a cyclohexyl ring or Representative primary amines which can be employed are methylamine, ethylamine, fluoro-, or chloro-, ethyl-amines in which the 2-carbon atom has from 1 to 2 halogen substituents which can be the same or different, the propyl-, buty]-, pentyl-, hexyl-, heptyl-,' octyl-, nonyl-, decyl-, undecyl-, dodecyl-, tridecylg tetradecyl-, pentadecyl-, hexadecyl-, heptadecyl-, octadecyl, nonadecylor eicosyl-amines, cyclopentyl-, cyclohexyl-, cycloheptylor cycloctyl-amines, or their halogen, cyano, alkoxy or hydrocarbon-substituted derivatives. It is to be understood that the primary amino group, or any open chain amine containing three carbon atoms or more, need not be on a terminal carbon atom.

Typical of the alkanolamines which can be used are HOCH CH NH CH CHOHCH NH group, and can have either straight or branched chain alkylene or oxaalkylene groups or hydroxycycloaliphatic amines such as S OH mines containing chlorine, cyano or alkoxy substituents can also be employed as reactants.

With primary amino alkanols the two types of compounds are formed one of which has the common formula alkylene or cycloalkylene-OH ition of $0 The novel compounds of thisinvention are all solid at room temperature and usually white in color when prepared and purified. On standing, some tend to turn slightly yellow due to decomposition. Some of the compounds can be sublimed and thus can be obtained in a .very high degree of purity. The primary monoamines which can be employed in.

and which are formed by reacting a large excess of S0 with an alkanol amine of the formula H N-aIkyIene-OH and the second type has the common formula 0 0 HO- -N- O-H Nalkylene- 0H or eycloalkylene alkylene or eycloalkylene-OH which are formed by reacting an excess of primary aminoalkanol with S0 The products formed with primary monoamines have the common formula These compounds are formed by using an excess of S is the rsastio mist irs..-

The reaction can be effected with or without an inert diluent, but a diluent which is a solvent for S0 and the amine is preferred. If no diluent is employed it is difficult to control the concentrations of the reactants unless the SO is liquefied, and in such event the heat generated by the reaction is removed only with some difficulty. Representative inert diluents include the liquid hydrocarbons such as petroleum fractions, or pure aliphatic hydrocarbons of -10 carbon atoms benzenoid hydrocarbons such as benzene, toluene, xylene or durene, the liquid aliphatic ethers, or alcohols or halogenerated hydrocarbons. The latter are preferred because they can be readily obtained in substantially anhydrous conditions and are easily dried, if contaminated with small amounts of water. Another advantage of using certain liquid halogenated hydrocarbons as diluents is that the new compounds are practically insoluble in them, so that they can be readily separated therefrom by filtration. Representative halogenated diluents are CH CI CH Br Cl-l ClBr, CCl CH CH CI, CH ClCH Cl, CH CliCl or chlorobenzene. Particularly preferred is @1 0 For the preparation of the compounds of this invention in which a non-hydroxylated primary amine is a reactant it is essential only to commingle a stoichiometric excess of S0 with the primary monoamine under sub-.

stantially anhydrous and oxygen-free conditions. The reaction takes place very rapidly with heat generation. The molar ratio of reactants should be in excess of two mols of S0 for every three mols of amine, and preferably about 1.2 2.5 mols of S0 are employed per mol of amine. Molar amounts of S0 greater than 2.5 per mol of amine are operative, but there is no advantage in using such large excesses of the reactant. With hydroxylated amines the molar ratio of S0 to amine can range from 3 to 1 to about 1 to 3, respectively. If the hydroxylated amine is present in molar excess the predominant compound is an imidodisulfinic acid bis(hydroxylamine) salt and if the S0 is in excess the predominant compound is an imidodisulfinic acid mono(- hydroxylamine) salt. I g

The reaction will proceed at any temperature from that at which S0 is liquid at atmospheric pressure up to the decomposition point of the salts. Temperatures ranging from to about 100C are operable. However, for practical reasons and economy, it is preferred to operate at temperatures of lO50C. In this range the reaction proceeds rapidly, S0 is sufficiently soluble in the diluent to assure proper concentration for the reaction desired and the heat of reaction can be re moved with readily available cooling water. if the solid' The examples which follow are intended to illustrate the invention, not to limit it. All parts are by weight unless otherwise specifically indicated.

EXAMPLE 1 A one-liter three-necked flask equipped with a stir-. rer, a condenser and inlets for amine and S0 and an; outlet for excess S0 which passed into a cold trap that was cooled with solid CO was charged with 500 ml. of methylene chloride. The temperature of the solvent was 23C. About 26.5 parts of S0 were fed into the reactor over a period of 15 minutes to saturate the methylene chloride and flush out air. Methyl amine was then added slowly without shuttingofi' the S0 supply. Over a period of three hours 34.5 parts of the amine and an additional 122 parts of S0 were fed to the reactor at a rate such that the S0 was in stoichiometric excess. The mixture was stirred continuously during this period. The reaction flask was kept cool by immersing it in a water bath to which ice was added as needed. The

O O CHsNHa O -N- -O HaNCHa compound was found to contain 27.7 percent S and about 0.9 percent Cl, which indicates that traces of solvent were still present. The melting point was 1 l0l 15C. Infrared analysis confirmed that the compound had the above structure.

XA LZ The equipment and process steps were the same as those described in Example 1. In this run a total of 108 parts of ethylamine and 187 parts of S0 were fed to the reactor which contained 686 parts of CH Cl The actual reaction period was about 2% hours. The dried white crystals of melted at 8l84C. One hundred eighty-two parts of the compound were recovered. This represents a yield of 86.6 percent based on the amine reactant. On analy-' sis it was found to contain 25.7 percent i 0.9 percent S, and 0.6 percent Cl.

Infrared analysis confirmed the above structure for this compound.

EXAMPLE 3 The reactor described above was charged with 685 parts Cl-hCl and then flushed and saturated with 30 parts S0 Cyclohexylamine was added slowly, together with S0 until an additional parts S0 and 107 parts C ll NH were fed into the reactor. The solids of sublimes at 172C. The yield on the cyclohexylamine fed was 86.6 percent of theory.

Infrared analysis confirmed the structure for the compound.

EXAMPLE 4 The reactor was charged with 680 parts CH Cl and flushed with S Thereafter 87 parts of n-butyl amine and 168 parts of S0 were fed to the reactor over a period of about 3% hours. The temperature wasmaintained at about 20-25C. A total of 120 parts of a dry compound having the structure were recovered. The product was slightly yellow in color. The yield based on the n-butyl amine fed was 87.2 percent.

EXAMPLE The apparatus of Example 1 was employed. The re-a actor was charged with 500 ml. Cl-l Cl and 29 grams. of S0 were fed into thereactor over a period of 22 minutes. Monoethanolamine was then charged to the? reactor along with S0 Over a period of 80 minutes I28 grams of the alkanolamine and an additional 129 grams of S0 were charged. Toward the end of the re-. action the slurry became too thick to stir. The mixture was filtered in the absence of air washed with 73 g. CH Cl and the solids were swept with N overnight. The recovered white solid weighed 258 g. Analysis showed the product to contain by weight 24.3 percentsulfur. This corresponds to a mixture of 74 mole per-' cent of the 2:2 adduct 0 o omoncrrmmoQ-m-Lon HicmoH' and 26 mole percent of the 3:2 adduct EXAMPLE 7 and solids was swept with nitrogen for 24 hours, to remove CHgClg as a vapor. The white solids remaining weighed g. and contained 22.0 percent S by analysis. This sulfur content corresponds to 79 percent of the 2:2 adduct and 21 percent of the amine 3:2 S0 adduct.

Substitution of other primary amines as defined above, for those of the specific examples results in the formation of the corresponding bis(aliphaticammonium) aliphatic imidosulfinic acids.

We claim:

ll. A composition of the formula RrNHa O HaNR;

wherein R,, R and R each is selected from the class consisting of open chain saturated hydrocarbon groups' having 1 to 20 C atoms, cycloaliphatic hydrocarbon groups having 5 to 8 ring C atoms, and halogen substituted aliphatic hydrocarbon groups having from 2 to 6 C atoms.

2. The composition of claim 1 in which R,, R and R each is saturated aliphatic hydrocarbon group of from I to 20 C atoms.

3. The composition of claim 1 in which each R,, R and R is an alkyl group of from 1 to 6 C atoms.

4. The composition of claim! in which R R and R is each a halogenated alkyl group of from 1 to 6 C atoms.

5. The composition of claim 1 in which each R R and R each is a cycloalkyl group of from 5 to 8 C atoms.

6. The composition of claim 1 in which R R and R is each a methyl group.

7. The composition of claim 1 in which R R and R is each an ethyl group.

8. The composition of claim 1 in which R R and R is each a n-butyl group.

9. The composition of claim 1 in which R,, R and R is each a cyclohexyl group.

10. A- method of preparing compounds of the structure II II R1NH3 OSNSO H3NR3 in which R R and R each is selected from the class consisting of open chain saturated hydrocarbon groups having 1 to 20 C atoms, cycloaliphatic hydrocarbon groups having 5 to 8 C atoms, and halogen substituted aliphatic hydrocarbon groups having from 2 to 6 C atoms, comprising simultaneously commingling a member of the class consisting of saturated aliphatic primary hydrocarbon amines having 1 to 20 C atoms, cy-

cloaliphatic hydrocarbon amines of 5 to 8 C atoms and b in reat r th n. saiqa a sqa ainias.qsmp n 11. The method o f claim 1 0 in whic h the reaction 7 8 temperature is between 25 and 100C. clohexylamine.

12. The method of claim 10 in which the amine and 16. The method of claim 10 in which the amine is S are fed into a reactor sirnultaneot sly. methyl amine.

13. The method of claim 10 in which the amine is a 17, The method of claim 10 in which the amine is primary alkyl amine. 5 ethyl amine.

14. The method of claim in which the amine is a 18. The method of claim 10 in which the amine is halogen-substituted alkyl amine of from 2 to 6 C atoms. butyl an ing V 7 U k nJfiamethe923921 1119 in whisk 9 1921 2112. i592;

@ 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 722 Dated OCtOber' 22, 1974- Invent0r(s) Ludo K. Frevel; Leonard J. Kressley It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, line 1, delete "AMINDOSULF'INIC" and insert -AMIDOSULFINIC- -r- Cover page, line 1 of first column, in the title, delete AMINDOSULFINIC" and insert -AMIDOSULFINIC- Cover page, column 2, fifth line of Abstract, delete "reacts" and insert -react-- Signed and sealed this 14th day of January 1975.

(SEAL) Attest:

McCOY M. GIBSON JR. c. MARSHALL DANN Attesting Officer Commissioner of Patents 

1. A COMPOSITION OF THE FORMULA
 2. The composition of claim 1 in which R1, R2 and R3 each is saturated aliphatic hydrocarbon group of from 1 to 20 C atoms.
 3. The composition of claim 1 in which each R1, R2 and R3 is an alkyl group of from 1 to 6 C atoms.
 4. The composition of claim 1 in which R1, R2 and R3 is each a halogenated alkyl group of from 1 to 6 C atoms.
 5. The composition of claim 1 in which each R1, R2 and R3 each is a cycloalkyl group of from 5 to 8 C atoms.
 6. The composition of claim 1 in which R1, R2 and R3 is each a methyl group.
 7. The composition of claim 1 in which R1, R2 and R3 is each an ethyl group.
 8. The composition of claim 1 in which R1, R2 and R3 is each a n-butyl group.
 9. The composition of claim 1 in which R1, R2 and R3 is each a cyclohexyl group.
 10. A method of preparing compounds of the structure
 11. The method of claim 10 in which the reaction temperature is between -25* and 100*C.
 12. The method of claim 10 in which the amine and SO2 are fed into a reactor simultaneously.
 13. The method of claim 10 in which the amine is a primary alkyl amine.
 14. The method of claim 10 in which the amine is a halogen-substituted alkyl amine of from 2 to 6 C atoms.
 15. The method of claim 10 in which the amine is cyclohexylamine.
 16. The method of claim 10 in which the amine is methyl amine.
 17. The method of claim 10 in which the amine is ethyl amine.
 18. The method of claim 10 in which the amine is butyl amine. 